WO2018101214A1 - 全芳香族液晶ポリエステル樹脂 - Google Patents
全芳香族液晶ポリエステル樹脂 Download PDFInfo
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- WO2018101214A1 WO2018101214A1 PCT/JP2017/042448 JP2017042448W WO2018101214A1 WO 2018101214 A1 WO2018101214 A1 WO 2018101214A1 JP 2017042448 W JP2017042448 W JP 2017042448W WO 2018101214 A1 WO2018101214 A1 WO 2018101214A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/12—Polymer mixtures characterised by other features containing additives being liquid crystalline or anisotropic in the melt
Definitions
- the present invention relates to a wholly aromatic liquid crystal polyester resin. Furthermore, the present invention relates to a wholly aromatic liquid crystal polyester resin composition containing the wholly aromatic liquid crystal polyester resin, a molded article and an electronic component comprising the composition.
- the wholly aromatic liquid crystal polyester resin is excellent in moldability and heat resistance
- molded products for example, injection molded products
- the wholly aromatic liquid crystal polyester resin is required to have more excellent moldability (thin wall portion filling property) and heat resistance.
- Patent Document 1 proposes a wholly aromatic liquid crystal polyester resin that can be melt-processed with an oxybenzoyl moiety as a main constituent part.
- Patent Document 2 proposes a wholly aromatic liquid crystal polyester resin capable of suppressing the generation of blisters.
- Patent Document 1 As preferred embodiments, 58 to 62 mol% of oxybenzoyl moiety, 2 to 5 mol% of 6-oxy-2-naphthoyl moiety, 1.5 to 11 mol% of 1,4-dioxyphenylene are preferred.
- a wholly aromatic liquid crystalline polyester resin comprising a portion, 11.5 to 22 mole percent 4,4'-dioxyphenyl portion, and 16.5 to 20 mole percent dicarboxyaryl moiety, A resin is described in which the molar concentration of the oxyphenylene moiety does not exceed the molar concentration of the 4,4′-dioxyphenyl moiety.
- the present inventors have found that the wholly aromatic liquid crystal polyester resin having the composition ratio described in Patent Document 1 is not sufficient in terms of improving moldability while maintaining heat resistance.
- Patent Document 2 as preferred embodiments, 30 to 45 mol% of an oxybenzoyl moiety, 3 to 9 mol% of a 6-oxy-2-naphthoyl moiety, 13 to 20 mol% of a 1,4-dioxyphenylene moiety, A wholly aromatic liquid crystal polyester resin comprising 10 to 17 mol% of 4,4′-dioxyphenyl moiety and 25 to 25 mol% of dicarboxyaryl moiety, wherein the molar concentration of 1,4-dioxyphenylene moiety A resin is described in which is higher than the molar concentration of the 4,4′-dioxyphenyl moiety.
- the present inventors have found that the wholly aromatic liquid crystal polyester resin having the composition ratio described in Patent Document 2 is insufficient in both heat resistance and moldability and needs to be improved.
- the present inventors can solve the above-mentioned problems by combining the constituent units contained in the wholly aromatic liquid crystal polyester resin with specific constituent units and composition ratios. And gained knowledge.
- the present invention is based on such knowledge.
- an object of the present invention is to provide a wholly aromatic liquid crystal polyester resin capable of achieving both excellent moldability and heat resistance.
- the wholly aromatic liquid crystal polyester resin according to the present invention is A wholly aromatic liquid crystal polyester resin comprising structural units represented by the following formulas (I) to (V) as essential structural units,
- the composition ratio (mol%) of the structural units (I) to (V) in the wholly aromatic liquid crystal polyester is as follows: 50 mol% ⁇ constituent unit (I) ⁇ 75 mol% 6 mol% ⁇ constituent unit (II) ⁇ 20 mol% 1 mol% ⁇ constituent unit (III) ⁇ 21.5 mol% 0.5 mol% ⁇ constituent unit (IV) ⁇ 10.5 mol% 2.5 mol% ⁇ constituent unit (V) ⁇ 22 mol% Structural unit (III)> Structural unit (IV)
- the composition ratio (mol%) of the structural units (I) to (V) in the wholly aromatic liquid crystal polyester is as follows: 55 mol% ⁇ constituent unit (I) ⁇ 70 mol% 7 mol% ⁇ constituent unit (II) ⁇ 17 mol% 3 mol% ⁇ constituent unit (III) ⁇ 18 mol% 1 mol% ⁇ constituent unit (IV) ⁇ 9 mol% 4 mol% ⁇ constituent unit (V) ⁇ 19 mol% It is preferable to satisfy.
- the wholly aromatic liquid crystal polyester resin composition preferably has a melting point of 320 ° C. or higher and 355 ° C. or lower.
- the wholly aromatic liquid crystal polyester resin composition preferably has a supercooling degree of 35 ° C. or higher.
- the wholly aromatic liquid crystal polyester resin composition according to the present invention comprises the wholly aromatic liquid crystal polyester resin and an inorganic filler.
- the inorganic filler is preferably a fibrous filler and / or a plate-like filler.
- the content of the inorganic filler is preferably 100 parts by weight or less with respect to 100 parts by weight of the wholly aromatic liquid crystal polyester resin contained in the wholly aromatic liquid crystal polyester resin composition.
- the molded product according to the present invention comprises the wholly aromatic liquid crystal polyester resin composition.
- An electronic component according to the present invention comprises the wholly aromatic liquid crystal polyester resin composition.
- the present invention it is possible to provide a wholly aromatic liquid crystal polyester resin capable of achieving both excellent moldability and heat resistance.
- the polyester resin composition containing the wholly aromatic liquid crystal polyester resin it is possible to produce a molded product having a very thin thickness part, and to achieve high integration, thinning, and low profile of electronic parts. Can be realized.
- the molded product according to the present invention Due to the thinning of electronic parts, warping is likely to occur during the reflow process, causing defects, but the molded product according to the present invention generates warpage when heated at high temperatures such as in the reflow process. Can also be suppressed.
- the assembly process of a molded product such as a connector due to the thinning there is a problem that cracks occur in the weld when a force is applied to the weld of the molded product. In the molded product, the strength of the weld is increased, and the occurrence of cracks can be suppressed.
- the wholly aromatic liquid crystalline polyester resin according to the present invention is a wholly aromatic liquid crystalline polyester resin comprising structural units represented by the following formulas (I) to (V) as essential structural units, and is a wholly aromatic liquid crystalline polyester.
- the composition ratio (mol%) of the structural units (I) to (V) in the inside satisfies the following conditions. According to such a wholly aromatic liquid crystal polyester resin, both excellent moldability and heat resistance can be achieved. Furthermore, high mechanical strength, blister resistance and low warpage can be imparted to a molded article produced using the resin.
- the total of the structural units (I) to (V) is preferably 95 mol% or more and 100 mol% or less, and 99 mol% or more and 100 mol% with respect to the structural units of the entire wholly aromatic liquid crystal polyester resin. The following is more preferable.
- the melting point of the wholly aromatic liquid crystal polyester resin is preferably 320 ° C. or higher and 355 ° C. or lower, more preferably 325 ° C. or higher and 350 ° C. or lower. If melting
- the melting point is based on ISO11357-3 and ASTM D3418, and can be measured by using, for example, a differential scanning calorimeter (DSC) manufactured by Seiko Denshi Kogyo Co., Ltd.
- the temperature was increased from room temperature to 370 ° C. at a rate of temperature increase of 20 ° C./min, and after the wholly aromatic liquid crystal polyester resin was completely melted, the temperature was decreased to 50 ° C. at a rate of 10 ° C./min, and further 20 ° C./min.
- the apex of the endothermic peak obtained when the temperature is raised to 420 ° C. at a rate of is defined as the melting point (° C.).
- the degree of supercooling of the wholly aromatic liquid crystal polyester resin is preferably 35 ° C. or higher, more preferably 35 ° C. or higher and 60 ° C. or lower.
- the degree of supercooling can be measured, for example, by using a differential scanning calorimeter (DSC) manufactured by Seiko Denshi Kogyo.
- the wholly aromatic liquid crystal polyester resin comprises the structural unit (I), and the composition ratio (mol%) of the structural unit (I) in the wholly aromatic liquid crystal polyester is 50 mol% or more and 75 mol. % Or less.
- the composition ratio of the structural unit (I) is preferably 55 mol% or more and 70 mol% or less, more preferably 57 mol% or more and 67 mol% or less, and further preferably 60 mol% or more and 65 mol% or less. .
- Examples of the monomer that provides the structural unit (I) include p-hydroxybenzoic acid (HBA, the following formula (1)), acylated products, ester derivatives, acid halides, and the like.
- HBA p-hydroxybenzoic acid
- the wholly aromatic liquid crystal polyester resin comprises the above-described structural unit (II), and the composition ratio (mol%) of the structural unit (II) in the wholly aromatic liquid crystal polyester is 6 mol% or more and 20 mol. % Or less.
- the composition ratio of the structural unit (II) is preferably 7 mol% or more and 17 mol% or less, more preferably 9 mol% or more and 16 mol% or less, and further preferably 10 mol% or more and 15 mol% or less. .
- Examples of the monomer that provides the structural unit (II) include 6-hydroxy-2-naphthoic acid (HNA, the following formula (2)), acylated products, ester derivatives, and acid halides.
- HNA 6-hydroxy-2-naphthoic acid
- the wholly aromatic liquid crystal polyester resin comprises the above-described structural unit (III), and the composition ratio (mol%) of the structural unit (III) in the wholly aromatic liquid crystal polyester is 1 mol% or more and 21.21. 5 mol% or less.
- the composition ratio of the structural unit (III) is preferably 3 mol% or more and 18 mol% or less, more preferably 5 mol% or more and 15 mol% or less, and further preferably 7 mol% or more and 12 mol% or less. .
- Examples of the monomer that provides the structural unit (III) include hydroquinone (HQ, the following formula (3)), acylated products thereof, and the like.
- the wholly aromatic liquid crystal polyester resin comprises the above-described structural unit (IV), and the composition ratio (mol%) of the structural unit (IV) in the wholly aromatic liquid crystal polyester is 0.5 mol% or more. 10.5 mol% or less.
- the composition ratio of the structural unit (IV) is preferably 1 mol% or more and 9 mol% or less, more preferably 2 mol% or more and 8 mol% or less, and further preferably 3 mol% or more and 7 mol% or less. .
- Examples of the monomer that gives the structural unit (IV) include 4,4′-dihydroxybiphenyl (BP, the following formula (4)), acylated products thereof, and the like.
- the wholly aromatic liquid crystal polyester resin comprises the above-described structural unit (V), and the composition ratio (mol%) of the structural unit (V) in the wholly aromatic liquid crystal polyester is 2.5 mol% or more. It is 22 mol% or less.
- the composition ratio of the structural unit (V) is preferably 4 mol% or more and 19 mol% or less, more preferably 7 mol% or more and 17 mol% or less, and further preferably 10 mol% or more and 15 mol% or less. .
- Examples of the monomer that gives the structural unit (V) include terephthalic acid (TPA, the following formula (5)), ester derivatives thereof, and acid halides.
- the wholly aromatic liquid crystal polyester resin according to the present invention can be produced by polymerizing monomers represented by the above formulas (1) to (5) by a conventionally known method.
- the wholly aromatic liquid crystal polyester resin according to the present invention can be produced only by melt polymerization. It can also be produced by preparing a prepolymer by melt polymerization and further solid-phase polymerizing it.
- the monomers represented by the above formulas (1) to (5) are combined in a predetermined blending amount to 100 mol%, and the above formula is used. It is preferable to carry out the reaction under reflux of acetic acid in the presence of 1.05 to 1.15 molar equivalents of acetic anhydride, based on the total hydroxyl groups of the monomers represented by (1) to (4).
- the prepolymer obtained by melt polymerization is cooled and solidified and then pulverized into powder or flakes, and then a known solid phase polymerization method is used.
- a method of heat-treating the prepolymer resin for 1 to 30 hours in a temperature range of 200 to 350 ° C. in an inert atmosphere such as nitrogen or under vacuum is preferably selected.
- the solid phase polymerization may be performed with stirring, or may be performed in a standing state without stirring.
- a catalyst may be used or may not be used.
- the catalyst to be used those conventionally known as polyester polymerization catalysts can be used, and metals such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide are used. Examples thereof include salt catalysts, nitrogen-containing heterocyclic compounds such as N-methylimidazole, and organic compound catalysts.
- the amount of the catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomers.
- the polymerization reaction apparatus in melt polymerization is not particularly limited, but a reaction apparatus used for reaction of a general high viscosity fluid is preferably used.
- reaction apparatuses include, for example, a stirring tank type polymerization reaction apparatus having a stirrer having various types of stirrer blades, a vertical type, a multistage type, a spiral band type, a helical shaft type, or the like, or And a kneader, a roll mill, a Banbury mixer, and the like, which are generally used for resin kneading.
- the wholly aromatic liquid crystal polyester resin composition according to the present invention comprises the above wholly aromatic liquid crystal polyester resin and an inorganic filler.
- the content of the inorganic filler in the wholly aromatic liquid crystal polyester resin composition is preferably 100 parts by weight or less with respect to 100 parts by weight of the wholly aromatic liquid crystal polyester resin contained in the wholly aromatic liquid crystal polyester resin composition.
- the amount is more preferably 10 to 70 parts by weight, and further preferably 20 to 55 parts by weight.
- an inorganic filler contained in a wholly aromatic liquid crystal polyester resin composition for example, fibrous, plate-like or powdery ones can be used, and these may be used in combination. Especially, it is preferable to use together a fibrous filler and a plate-shaped filler.
- the inorganic filler include glass fiber, milled glass, silica alumina fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate whisker, aluminum borate whisker, wollastonite, talc, mica, graphite, calcium carbonate, Examples thereof include dolomite, clay, glass flakes, glass beads, barium sulfate and titanium oxide, and the wholly aromatic liquid crystal polyester resin composition may contain one or more of these.
- the wholly aromatic liquid crystal polyester resin composition according to the present invention may contain a resin other than the wholly aromatic liquid crystal polyester resin as long as the effects of the present invention are not impaired.
- a resin other than the wholly aromatic liquid crystal polyester resin for example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyamide, polyimide, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polytetrafluoroethylene and the like, and wholly aromatic liquid crystal polyester resin composition is One or more of these may be included.
- the wholly aromatic liquid crystal polyester resin composition according to the present invention has other additives such as a colorant, a dispersant, a plasticizer, an antioxidant, a flame retardant, a heat stabilizer, as long as the effects of the present invention are not impaired.
- a colorant such as a colorant, a dispersant, a plasticizer, an antioxidant, a flame retardant, a heat stabilizer, as long as the effects of the present invention are not impaired.
- An ultraviolet absorber, an antistatic agent, and a surfactant may be included.
- a wholly aromatic liquid crystal polyester resin composition is obtained by melt-kneading a wholly aromatic liquid crystal polyester resin with a filler and the like using a Banbury mixer, kneader, single screw or twin screw extruder, etc. Can do.
- the melting point is 280 ° C. to 360 ° C., and the melting point is 1 ⁇ 10 2 Pa ⁇ s or less at a shear rate of 1000 sec-1 when the melting point is + 20 ° C.
- a liquid crystal polyester resin other than the wholly aromatic liquid crystal polyester resin may be blended in an amount of 1 to 100 parts by weight.
- the molded product according to the present invention comprises the wholly aromatic liquid crystal polyester resin composition.
- the molded product of the present invention is excellent in shape stability, and for example, even when heat is applied in the reflow process, warping of the molded product can be suppressed.
- the molded product according to the present invention can be produced by injection molding or extrusion molding of the wholly aromatic liquid crystal polyester resin composition.
- the molded product according to the present invention may be a film shape, a sheet shape, a thread shape, a nanofiber, and a non-woven fabric.
- Specific film forming methods include inflation molding, melt extrusion molding, solution cast molding, and the like.
- the film thus obtained may be a single layer film made of a wholly aromatic polyester resin composition or a multilayer film with different materials.
- a film obtained by melt extrusion molding or solution casting may be stretched uniaxially or biaxially.
- you may heat-process in order to remove the anisotropy of these films.
- the electronic component according to the present invention comprises the wholly aromatic liquid crystal polyester resin composition.
- electronic components include high-speed transmission connectors, CPU sockets, Board to Board connectors, circuit boards, flexible circuit boards, laminated circuit boards, anti-collision radars, RFID tags, capacitors, inverter parts, insulating films, lithium ions Examples thereof include an insulating material for a secondary battery such as a battery, a speaker diaphragm, a camera module, and the like.
- these electronic components include a molded product (for example, an injection molded product) or a film made of a wholly aromatic liquid crystal polyester resin composition.
- Example 1 Totally aromatic liquid crystal polyester resin A
- HBA p-hydroxybenzoic acid
- HNA 6-hydroxy-2-naphthoic acid
- HQ hydroquinone
- BP 4,4′-dihydroxybiphenyl
- TPA terephthalic acid
- the polymerization vessel in acetic acid distillation was heated at 0.5 ° C./min, and when the melt temperature in the tank reached 310 ° C., the polymer was taken out and cooled and solidified.
- the obtained polymer was pulverized and pulverized to a size passing through a sieve having an aperture of 1.0 mm to obtain a prepolymer.
- the prepolymer obtained above is filled into a glass tube oven manufactured by Shibata Kagaku, and the heater temperature is raised from room temperature to 290 ° C. over 12 hours while rotating, and then the temperature is maintained at 290 ° C. for 1 hour.
- the solid phase polymerization was performed. Thereafter, natural heat was radiated at room temperature while rotating the tank to obtain a wholly aromatic liquid crystal polyester resin A.
- a polarizing microscope BH-2 manufactured by Olympus Corporation equipped with a hot stage FP82HT for microscopes manufactured by METTLER a polyester sample was heated and melted on a microscope heating stage, and liquid crystallinity was confirmed from the presence or absence of optical anisotropy. .
- Example 2 Totally aromatic liquid crystal polyester resin B
- a liquid crystal polyester resin B was obtained in the same manner as in Example 1 except that the monomer charge was changed to 62 mol% HBA, 10 mol% HNA, 10 mol% HQ, 4 mol% BP, and 14 mol% TPA. The sex was confirmed.
- Example 3 Totally aromatic liquid crystal polyester resin C
- a liquid crystal polyester resin C was obtained in the same manner as in Example 1 except that the monomer charge was changed to 60 mol% HBA, 10 mol% HNA, 8 mol% HQ, 7 mol% BP, and 15 mol% TPA. The sex was confirmed.
- Example 4 wholly aromatic liquid crystal polyester resin D
- a liquid crystal polyester resin D was obtained in the same manner as in Example 1 except that the monomer charge was changed to 62 mol% HBA, 10 mol% HNA, 8.5 mol% HQ, 5.5 mol% BP, and 14 mol% TPA. Similarly, liquid crystal properties were confirmed.
- Example 5 wholly aromatic liquid crystal polyester resin E
- a liquid crystal polyester resin E was obtained in the same manner as in Example 1 except that the monomer charge was changed to 62 mol% HBA, 15 mol% HNA, 10.5 mol% HQ, 1 mol% BP, and 11.5 mol% TPA. Similarly, liquid crystal properties were confirmed.
- Example 2 Totally aromatic liquid crystal polyester resin G
- a liquid crystal polyester resin G was obtained in the same manner as in Example 1 except that the monomer charge was changed to 62 mol% HBA, 10 mol% HNA, 7 mol% HQ, 7 mol% BP, and 14 mol% TPA. The sex was confirmed.
- the molded product obtained as described above is allowed to stand in an air oven maintained at 260 ° C. for 10 minutes, and the warped amount of the molded product after heating is set to a one-shot 3D macroscope (manufactured by Keyence Corporation, trade name: VR-3100).
- the measurement of the warp is done by measuring the highest and the lowest positions of the arrow shown in Fig. 2 from the top with the 3D microscope when the molded product is placed with the bottom surface (surface for measuring warp) facing upward. The difference was defined as the amount of warpage.
- the measurement results are summarized in Table 2. The better the shape stability, the smaller the warp amount, and the warp amount is preferably 40 ⁇ m or less.
Abstract
Description
近年、パーソナル・コンピューターやスマートフォンなどの小型化から電子部品の高集積化、薄肉化、低背化が進んでおり、非常に薄い肉厚部を有する成形品の需要が高まっている。そのため、全芳香族液晶ポリエステル樹脂には、より優れた成形性(薄肉部充填性)や耐熱性が求められている。例えば、特許文献1には、オキシベンゾイル部分を主要な構成部分とする溶融加工可能な全芳香族液晶ポリエステル樹脂が提案されている。
必須の構成単位として下記式(I)~(V)で表される構成単位を含んでなる全芳香族液晶ポリエステル樹脂であって、
50モル%≦構成単位(I)≦75モル%
6モル%≦構成単位(II)≦20モル%
1モル%≦構成単位(III)≦21.5モル%
0.5モル%≦構成単位(IV)≦10.5モル%
2.5モル%≦構成単位(V)≦22モル%
構成単位(III)>構成単位(IV)
を満たすことを特徴とする、全芳香族液晶ポリエステル樹脂。
55モル%≦構成単位(I)≦70モル%
7モル%≦構成単位(II)≦17モル%
3モル%≦構成単位(III)≦18モル%
1モル%≦構成単位(IV)≦9モル%
4モル%≦構成単位(V)≦19モル%
を満たすことが好ましい。
本発明による全芳香族液晶ポリエステル樹脂は、必須の構成単位として下記式(I)~(V)で表される構成単位を含んでなる全芳香族液晶ポリエステル樹脂であって、全芳香族液晶ポリエステル中における構成単位(I)~(V)の組成比(モル%)は、下記の条件を満たす。このような全芳香族液晶ポリエステル樹脂によれば、優れた成形性および耐熱性を両立することができる。さらに、該樹脂を使用し製造した成形品に対し、高い機械的強度、および耐ブリスター性ならびに低ソリ性を付与することができる。
6モル%≦構成単位(II)≦20モル%
1モル%≦構成単位(III)≦21.5モル%
0.5モル%≦構成単位(IV)≦10.5モル%
2.5モル%≦構成単位(V)≦22モル%
構成単位(III)>構成単位(IV)
融点は、ISO11357-3、ASTM D3418に準拠するものであり、例えば、セイコー電子工業(株)製の示差走査熱量計(DSC)を用いることにより測定することができる。
なお、昇温速度20℃/分で室温から370℃まで昇温し、全芳香族液晶ポリエステル樹脂を完全に融解させたあと、速度10℃/分で50℃まで降温し、更に20℃/分の速度で420℃まで昇温するときに得られる吸熱ピークの頂点を融点(℃)とする。
過冷却度は、例えば、セイコー電子工業(株)製の示差走査熱量計(DSC)を用いることにより測定することができる。
なお、昇温速度20℃/分で室温から370℃まで昇温し、全芳香族液晶ポリエステル樹脂を完全に融解させたあと、速度10℃/分で50℃まで降温した時に得られる発熱ピークの頂点を結晶化温度Tc(℃)とし、更に20℃/分の速度で420℃まで昇温するときに得られる吸熱ピークの頂点を融点Tm(℃)とし、「Tm(℃)-Tc(℃)」を過冷却度(℃)とした。
全芳香族液晶ポリエステル樹脂は、上記の構成単位(I)を含んでなるものであり、全芳香族液晶ポリエステル中における構成単位(I)の組成比(モル%)は、50モル%以上75モル%以下である。構成単位(I)の組成比は、好ましくは55モル%以上70モル%以下であり、より好ましくは57モル%以上67モル%以下であり、さらに好ましくは60モル%以上65モル%以下である。
全芳香族液晶ポリエステル樹脂は、上記した構成単位(II)を含んでなるものであり、全芳香族液晶ポリエステル中における構成単位(II)の組成比(モル%)は、6モル%以上20モル%以下である。構成単位(II)の組成比は、好ましくは7モル%以上17モル%以下であり、より好ましくは9モル%以上16モル%以下であり、さらに好ましくは10モル%以上15モル%以下である。
全芳香族液晶ポリエステル樹脂は、上記した構成単位(III)を含んでなるものであり、全芳香族液晶ポリエステル中における構成単位(III)の組成比(モル%)は、1モル%以上21.5モル%以下である。構成単位(III)の組成比は、好ましくは3モル%以上18モル%以下であり、より好ましくは5モル%以上15モル%以下であり、さらに好ましくは7モル%以上12モル%以下である。
全芳香族液晶ポリエステル樹脂は、上記した構成単位(IV)を含んでなるものであり、全芳香族液晶ポリエステル中における構成単位(IV)の組成比(モル%)は、0.5モル%以上10.5モル%以下である。構成単位(IV)の組成比は、好ましくは1モル%以上9モル%以下であり、より好ましくは2モル%以上8モル%以下であり、さらに好ましくは3モル%以上7モル%以下である。
全芳香族液晶ポリエステル樹脂は、上記した構成単位(V)を含んでなるものであり、全芳香族液晶ポリエステル中における構成単位(V)の組成比(モル%)は、2.5モル%以上22モル%以下である。構成単位(V)の組成比は、好ましくは4モル%以上19モル%以下であり、より好ましくは7モル%以上17モル%以下であり、さらに好ましくは10モル%以上15モル%以下である。
本発明に係る全芳香族液晶ポリエステル樹脂は、上記式(1)~(5)で表されるモノマーを、従来公知の方法で重合することにより製造することができる。
例えば、本発明に係る全芳香族液晶ポリエステル樹脂は、溶融重合のみによって製造することができる。また、溶融重合によりプレポリマーを作製し、これをさらに固相重合することによっても製造することができる。
本発明による全芳香族液晶ポリエステル樹脂組成物は、上記全芳香族液晶ポリエステル樹脂と、無機充填剤とを含んでなる。
中でも、繊維状充填剤および板状充填剤を合わせて使用することが好ましい。
無機充填剤としては、例えば、ガラス繊維、ミルドガラス、シリカアルミナ繊維、アルミナ繊維、炭素繊維、アラミド繊維、チタン酸カリウムウイスカ、ホウ酸アルミニウムウイスカ、ウォラストナイト、タルク、マイカ、グラファイト、炭酸カルシウム、ドロマイト、クレイ、ガラスフレーク、ガラスビーズ、硫酸バリウムおよび酸化チタンなどが挙げられ、全芳香族液晶ポリエステル樹脂組成物は、これらを1種または2種以上含んでいてもよい。
全芳香族液晶ポリエステル樹脂組成物は、全芳香族液晶ポリエステル樹脂に、充填剤などを配合したものを、バンバリーミキサー、ニーダー、一軸または二軸押出機などを用いて、溶融混練することにより得ることができる。
本発明による成形品は、上記の全芳香族液晶ポリエステル樹脂組成物を含んでなるものである。本発明の成形品は、形状安定性に優れるものであり、例えば、リフロー工程において熱が加わる場合であっても、成形品のソリを抑制することができる。
本発明による電子部品は、上記全芳香族液晶ポリエステル樹脂組成物を含んでなる。電子部品としては、例えば、高速伝送用コネクタ、CPUソケット、Board to Boardコネクタ、回路基板、フレキシブル回路基板、積層用回路基板、衝突防止用レーダー、RFIDタグ、コンデンサー、インバーター部品、絶縁フィルム、リチウムイオン電池などの二次電池の絶縁材、スピーカー振動板、カメラモジュールなどが挙げられる。具体的には、これら電子部品は、全芳香族液晶ポリエステル樹脂組成物からなる成形品(例えば、射出成形品)やフィルムなどを備えてなる。
[実施例1:全芳香族液晶ポリエステル樹脂A]
攪拌翼を有する重合容器にp-ヒドロキシ安息香酸(HBA)62モル%、6-ヒドロキシ-2-ナフトエ酸(HNA)10モル%、ハイドロキノン(HQ)8モル%、4,4’-ジヒドロキシビフェニル(BP)6モル%、テレフタル酸(TPA)14モル%を加え、触媒として酢酸カリウムおよび酢酸マグネシウムを仕込み、重合容器の減圧-窒素注入を3回行って窒素置換を行った後、無水酢酸(全水酸基に対して1.08モル当量)を更に添加し、150℃まで昇温し、還流状態で2時間アセチル化反応を行った。
モノマー仕込みを、HBA62モル%、HNA10モル%、HQ10モル%、BP4モル%、TPA14モル%に変更した以外は実施例1と同様にして、液晶ポリエステル樹脂Bを得て、上記と同様にして液晶性を確認した。
モノマー仕込みを、HBA60モル%、HNA10モル%、HQ8モル%、BP7モル%、TPA15モル%に変更した以外は実施例1と同様にして、液晶ポリエステル樹脂Cを得て、上記と同様にして液晶性を確認した。
モノマー仕込みを、HBA62モル%、HNA10モル%、HQ8.5モル%、BP5.5モル%、TPA14モル%に変更した以外は実施例1と同様にして、液晶ポリエステル樹脂Dを得て、上記と同様にして液晶性を確認した。
モノマー仕込みを、HBA62モル%、HNA15モル%、HQ10.5モル%、BP1モル%、TPA11.5モル%に変更した以外は実施例1と同様にして、液晶ポリエステル樹脂Eを得て、上記と同様にして液晶性を確認した。
モノマー仕込みを、HBA62モル%、HNA4モル%、HQ5モル%、BP12モル%、TPA17モル%に変更した以外は実施例1と同様にして、液晶ポリエステル樹脂Fを得て、上記と同様にして液晶性を確認した。
モノマー仕込みを、HBA62モル%、HNA10モル%、HQ7モル%、BP7モル%、TPA14モル%に変更した以外は実施例1と同様にして、液晶ポリエステル樹脂Gを得て、上記と同様にして液晶性を確認した。
モノマー仕込みを、HBA62モル%、HNA10モル%、HQ4モル%、BP10モル%、TPA14モル%に変更した以外は実施例1と同様にして、液晶ポリエステル樹脂Hを得て、上記と同様にして液晶性を確認した。
モノマー仕込みを、HBA62モル%、HNA4モル%、HQ5モル%、BP12モル%、TPA17モル%に変更した以外は実施例1と同様にして、液晶ポリエステル樹脂Iを得て、上記と同様にして液晶性を確認した。
モノマー仕込みを、HBA60モル%、BP20モル%、TPA15モル%、イソフタル酸5モル%に変更した以外は実施例1と同様にして、液晶ポリエステル樹脂Jを得て、上記と同様にして液晶性を確認した。
実施例および比較例において得られた液晶ポリエステル樹脂の融点は、セイコー電子工業(株)製の示差走査熱量計(DSC)により測定した。このとき、昇温速度20℃/分で室温から370℃まで昇温してポリマーを完全に融解させた後、速度10℃/分で50℃まで降温するときに得られる発熱ピークの頂点を結晶化温度(Tc)とし、更に20℃/分の速度で420℃まで昇温するときに得られる吸熱ピークの頂点を融点(Tm)とし、「Tm(℃)-Tc(℃)」を過冷却度(℃)とした。測定結果を表1にまとめた。
実施例1と同じモノマー組成比のモノマー混合物に、触媒として酢酸カリウムおよび酢酸マグネシウムを加え、SUS316を材質とし、ダブルヘリカル攪拌翼を有する内容積6Lの重合槽へ仕込み、実施例1と同様の条件にてプレポリマーを得た。
次に、上記で得られたプレポリマーを固相重合装置に充填し、窒素を流通しながら、回転速度5rpmでヒーター温度を室温から150℃まで1時間かけて昇温した後、200℃まで2時間半かけて昇温し、更に250℃まで3時間半かけて昇温した。250℃で2時間保持した後、 更に290℃まで6時間半かけて昇温し、290℃で1時間保持し固相重合を行った。その結果、全芳香族液晶ポリエステル樹脂Aを得た。
上記のようにして得られた全芳香族液晶ポリエステル樹脂A100重量部に対し、繊維状充填剤(セントラルグラスファイバー(株)製、商品名:EFH150-01)7重量部および板状充填剤(マイカ、(株)ヤマグチマイカ製、商品名:AB-25S)36重量部を配合し、二軸押出機にて溶融混練したものをペレット化し、全芳香族液晶ポリエステル樹脂組成物Aを得た。
また、全芳香族液晶ポリエステル樹脂Aを参考例1で得られた全芳香族液晶ポリエステル樹脂Jに変更した以外は、同様にして全芳香族液晶ポリエステル樹脂組成物Jを得た。
上記のようにして得られた樹脂組成物Aのペレットを射出成形機(住友重機械工業(株)製、商品名:SG-25)を用いて、シリンダー温度を融点+10℃とし、金型温度を80℃とし、射出速度100mm/secで射出成形し、ASTM D790に準じた曲げ試験片(幅13mm、長さ130mm、厚さ3mm)を作製し曲げ強度を測定した。
また、樹脂組成物Jを用いて、同様に試験片を作製し、曲げ強度を測定した。測定結果を表2にまとめた。
上記のようにして得られた樹脂組成物Aのペレットを、射出成形機(Sodick製、商品名:LD10EH2)にて、シリンダー温度を融点+10℃とし、金型温度を80℃とし、射出速度150mm/secで射出成形し、JIS K7160 2形に準じた試験片(幅10mm、長さ60mm、厚さ0.4mm)を作製した。
また、樹脂組成物Jを用いて、同様に試験片を作製した。上記のようにして得られた試験片を所定の温度に保持したエアーオーブン中に30分間放置して、試験片表面にブリスターおよび変形の発生しない最高温度を耐ブリスター温度とした。測定結果を表2にまとめた。
上記のようにして得られた樹脂組成物Aのペレットを、射出成形機(Sodick製、商品名:LP20)にて、シリンダー温度を融点+10℃、金型温度100℃とし、射出速度150mm/secで、インサート成形により樹脂と金属部とを一体化して、図1および2に示す形状の成形品を得た。また、樹脂組成物Jを用いて、同様に成形品を得た。なお、図1には、得られた成形品の上面図と側面図を示し、図2には下面図を示す。寸法の数値の単位はmmである。
上記のようにして得られた成形品を260℃に保持したエアーオーブン中に10分間放置し、加熱後の成形品のソリ量をワンショット3Dマクロスコープ((株)キーエンス社製、商品名:VR-3100)を用いて測定した。ソリの測定は、成形品を下面(ソリを測定する面)を上向きにして置いた時の、図2に示した矢印部を3Dマイクロスコープにて上から、最も高い位置と低い位置を測定し、その差をソリ量とした。測定結果を表2にまとめた。なお、形状安定性が良いほどソリ量は小さくなり、ソリ量は40μm以下であることが好ましい。
上記のようにして得られた樹脂組成物Aのペレットを、射出成形機(住友重機械工業製、商品名:SE30DU)にて、シリンダー温度を融点+10℃とし、金型温度を100℃とし、射出速度250mm/secで射出成形し、図3に示す試験片(幅14.6mm、長さ48.0mm、厚さ0.35mm)を作製した。また、樹脂組成物Jを用いて、同様に試験片を作製した。
上記のようにして得られた試験片のウェルド部を、下記の3点曲げ試験の条件で上側から押圧し、ウェルド部が破断するときの応力を測定した。測定結果を表3にまとめた。
(3点曲げ試験の条件)
・スパン間距離=25mm
・治具R=10mm
・降下速度=1.27mm/min
Claims (9)
- 前記全芳香族液晶ポリエステル中における構成単位(I)~(V)の組成比(モル%)が、下記の条件:
55モル%≦構成単位(I)≦70モル%
7モル%≦構成単位(II)≦17モル%
3モル%≦構成単位(III)≦18モル%
1モル%≦構成単位(IV)≦9モル%
4モル%≦構成単位(V)≦19モル%
を満たす、請求項1に記載の全芳香族液晶ポリエステル樹脂。 - 融点が、320℃以上355℃以下である、請求項1または2に記載の全芳香族液晶ポリエステル樹脂。
- 過冷却度が、35℃以上である、請求項1~3のいずれか一項に記載の全芳香族液晶ポリエステル樹脂。
- 請求項1~4のいずれか一項に記載の全芳香族液晶ポリエステル樹脂と、無機充填剤とを含んでなる、全芳香族液晶ポリエステル樹脂組成物。
- 前記無機充填剤が、繊維状充填剤および/または板状充填剤である、請求項5に記載の全芳香族液晶ポリエステル樹脂組成物。
- 前記無機充填剤の含有量が、前記全芳香族液晶ポリエステル樹脂組成物に含まれる全芳香族液晶ポリエステル樹脂100重量部に対して、100重量部以下である、請求項5または6に記載の全芳香族液晶ポリエステル樹脂組成物。
- 請求項5~7のいずれか一項に記載の全芳香族液晶ポリエステル樹脂組成物を含んでなる、成形品。
- 請求項5~7のいずれか一項に記載の全芳香族液晶ポリエステル樹脂組成物を含んでなる、電子部品。
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CN110088166B (zh) | 2021-06-08 |
US20190300700A1 (en) | 2019-10-03 |
US10968347B2 (en) | 2021-04-06 |
KR102173693B1 (ko) | 2020-11-03 |
JP6411702B1 (ja) | 2018-10-24 |
TWI735708B (zh) | 2021-08-11 |
CN110088166A (zh) | 2019-08-02 |
TW201829534A (zh) | 2018-08-16 |
JPWO2018101214A1 (ja) | 2018-12-06 |
KR20190077004A (ko) | 2019-07-02 |
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